Chiral Diols Research Articles

キラルシントン法とは？ ホネキラルアセタールと有機合成

Homochiral acetals derived from chiral diol and carbonyl compound are recognized as “Chiralsynthon” of the carbonyl group, whose chirality enables to introduce a new asymmetric center into the molecule. The reaction is based on the selective coordination of the organometallic reagent or Lewis acid to one of the two acetal oxygen. Using thus obtained homochiral acetals this article surveys the recent development of asymmetric syntheses involving the selective cleavage of the acetal or induction of the asymmetry to neighboring functional group.

A polarimetric, circular dichroism and 11B nuclear magnetic resonance study of the reaction of the tetrahydroxyborate ion with two chiral 1,3-diols

The reactions of the chiral diols L-(+)-threo-2-amino-1-phenylpropane-1, 3-diol and D-(–)-threo-2-amino-1-(4-nitrophenyl)propane-1,3-diol with the tetrahydroxyborate ion, B(OH)–4, have been studied by polarimetry, circular dichroism and 11B n.m.r. The results show quite clearly that 1,3-diols can react with the B(OH)–4 ion. The equilibrium constants for the reactions derived from the polarimetric and n.m.r. studies are in quite good agreement and show that the substituted 1,3-diols react slightly more readily than propane-1,3-diol itself.

ChemInform Abstract: Group 4 Organometallic Reagents. Part 2. Enantiomeric Purity Determination of 1,2‐Diols Through NMR Spectroscopy without Chiral Auxiliaries.

AbstractThe e.e. of various mixtures of enantiomers of the Sn derivatives (Ib), obtained by treating chiral diols (Ia) with Bu2SnO, are determined (accuracy ± 2%) by means of 13C NMR spectroscopy.

ChemInform Abstract: An Easy Route to a Chiral Diol in the Furan Series from 2‐Deoxyaldohexoses.

AbstractErhitzen von 2‐Desoxy‐D‐glucose (Ia) oder ‐D‐ga1actose (Ib) mit Pyridiniumchlorid in Pyridin und nachfolgende Acetylierung liefern das Bis‐ acetat (IIa) des chiralen Glykols (IIb).

ChemInform Abstract: Preparation of the Chiral Diol (2R,3R)‐2‐Hydroxymethyl‐3‐hydroxy‐tetrahydropyran from D‐Glucose via Reductive Rearrangement of Pseudo‐D‐glucal Triacetate.

AbstractDie Hydrierung des Triacetats (I) unter der angegebenen Bedingung ergibt Gemische aus dem Diacetat (II) und dem Triacetat (III).

An Easy Route to a Chiral Diol in the Furan Series from 2-Deoxyaldohexoses

An Easy Route to a Chiral Diol in the Furan Series from 2-Deoxyaldohexoses

( S, S)-diisopropylethanediol (“DIPED”): A new chiral director for the α-chloro boronic ester synthesis

( S, S)-Diisopropylethanediol, “DIPED”, has been synthesized by means of our new general chiral diol synthesis based on α-chloro boronic esters, and has in turn been shown to be an effective chiral ( R) directing group in this synthesis, consistently yielding ( R)/( S)-ratios in the 25:1 to 30:1 range with a series of typical substrates.

Interaction of cytochrome P-450 with a hydroperoxide derived from butylated hydroxytoluene. Mechanism of isomerization.

Attack of O2 on the phenoxy radical derived from butylated hydroxytoluene resulted in the formation of 2,6-di-t-butyl-4-hydroperoxy-4-methyl-2,5-cyclohexadienone (BOOH). This hydroperoxide was rapidly consumed when incubated with rat liver microsomes in the absence of NADPH. The destruction of BOOH was accompanied by formation of the corresponding alcohol (BOH) and a derivative of the alcohol (B(OH)2) in which a t-butyl methyl group was hydroxylated. This diol was produced also when BOH was incubated with microsomes and NADPH, but at a slower rate. Mass spectral analyses of B(OH)2 formed from substrates labeled with either 2H or 18O, showed that oxygen was transferred from the peroxy group to a t-butyl group (via the heme iron of P-450) without migration of the intermediate alcohol from the enzyme active site. The results support a mechanism involving heterolytic O-O bond cleavage during isomerization of the hydroperoxide to B(OH)2. The chiral diol was produced from BOOH nonstereoselectively, but the NADPH/O2-supported hydroxylation of BOH resulted in the formation of a 20% excess of one enantiomer of B(OH)2. Analyses of products formed from the interaction of cumene hydroperoxide with cytochrome P-450 showed that this substrate undergoes rearrangement also; 2-phenyl-1,2-propanediol was produced, together with cumyl alcohol and acetophenone. These results indicate that isomerization competes with other pathways of hydroperoxide destruction by cytochrome P-450.

ChemInform Abstract: THE ASYMMETRIC ULLMANN COUPLING REACTION OF CHIRAL DIOL DIESTERS OF 1‐BROMO‐2‐NAPHTHOIC ACID AND 2‐HALO‐3‐NITROBENZOIC ACIDS: HIGHLY DIASTEREOSELECTIVE SYNTHESIS OF ATROPISOMERIC 6,6′‐DINITRODIPHENIC ACIDS

AbstractDie Cu‐katalysierte Ullmann‐Reaktion der aus den Komponenten (I) und (II) gebildeten chiralen Diol′‐ 25 ester (III)führt nach reduktiver Spaltung der Esterbindungen unter Bildung von l′,l′‐Binaphthylbindungen zu den chiralen Produkten (IVa)‐(IVc); im Falle des analog erhältlichen (IIId) wird kaum asymm. Induktion erreicht.

The Asymmetric Ullmann Coupling Reaction of Chiral Diol Diesters of 1-Bromo-2-naphthoic Acid and 2-Halo-3-nitrobenzoic Acids: Highly Diastereoselective Synthesis of Atropisomeric 6,6′-Dinitrodiphenic Acids

Abstract The copper-promoted Ullmann reaction of chiral diol diesters of 1-bromo-2-naphthoic acid induced axial dissymmetry into the newly formed 1,1′-binaphthyl bond: chiral diol, apparent net optical yield for the joining of two naphthyl units, and axial chirality induced are as follows: (S)-1,1′-binaphthyl-2,2′-diol, 71%, S; (1S,2S)-1,2-diphenyl-1,2-ethanediol, 32%, S; (1R,2R)-1,2-bis(ethoxycarbonyl)-1,2-ethanediol, 33%, S; (4S,5S)-bis(hydroxymethyl)-2,2-dimethyl-1,3-dioxolane, 3.7%, R. The reaction of (R)-1,1′-binaphthyl-2,2′-diol esters of 2-halo-3-nitrobenzoic acids gave up to 85% net optical yield for the coupling; the intramolecular cyclization proceeded with virtually complete diastereoselectivity to give cyclic diester of R,R-configuration in a 42% isolated yield. This remarkable stereocontrol is ascribed to the steric requirement of the 12-membered cyclic diester structure containing rigid 1,1′-binaphthyl and 1,1′-biphenyl moiety.

Phosgene —a versatile reagent for enantiomer separation by capillary gas chromatography

Phosgene has been used to form cyclic derivatives of chiral diols, α-hydroxy acids, N-methylamino acids and other di- and trifunctional compounds and the enantiomers then separated by gas chromatography on the chiral polysiloxane phase XE-60— L-valine—( R)-α-phenylethylamide. In this way phosgene can supplement the isocyanates as a versatile reagent for enantiomer separation.

Regioselective cyclodehydration of chiral diols with diethoxytriphenylphosphorane, triphenylphosphine-tetrachloromethane-potassium carbonate, and triphenylphosphine-diethyl azodicarboxylate reagents. A comparative study

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTRegioselective cyclodehydration of chiral diols with diethoxytriphenylphosphorane, triphenylphosphine-tetrachloromethane-potassium carbonate, and triphenylphosphine-diethyl azodicarboxylate reagents. A comparative studyPhilip L. Robinson, Carey N. Barry, S. Woody Bass, Susan E. Jarvis, and Slayton A. Evans Jr.Cite this: J. Org. Chem. 1983, 48, 26, 5396–5398Publication Date (Print):December 1, 1983Publication History Published online1 May 2002Published inissue 1 December 1983https://doi.org/10.1021/jo00174a059RIGHTS & PERMISSIONSArticle Views583Altmetric-Citations42LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (427 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

119Sn Nuclear magnetic resonance and mass spectrometric studies of the stannylenes of chiral and achiral diols: an interpretation of their regiospecific activation.

119 Sn n.m.r., and (in some cases) mass spectrometric studies of carbohydrate-derived chiral diols, and other ones, suggested that they are dimer with C-2 symmetry in all physical states (except, may be, in polar solvents), and this may be the origin of the unique nucleophilic enhancement of one oxygen atom to the parent diols.

Asymmetric reduction of ketones by using complexes of lithium tetrahydridoaluminate(III) with 1,4:3,6-dianhydro-D-mannitol and 1,3:4,6-di-O-benzylidene-D-mannitol

The use of chiral diols each containing a two-fold axis of symmetry to achieve asymmetric reductions of some ketones with metal hydrides is described. The symmetry of these complexes simplifies interpretation of the observed enantioselectivity.